Method of preventing electric charging of liquid hydrocarbons



United States Patent 3,359,086 METHOD OF PREVENTING ELECTRIC CHARG- ING 0F LIQUID HYDROCARBONS Hideo Marumo, Morio Ninomiya, and Yasushi Matsuzaki, Tokyo, and Makoto Takai, Chiba, Japan, assignors to Lion Yushi Kabushiki Kaisha No Drawing. Filed Feb. 1, 1965, Ser. No. 429,628

6 Claims. (CI. 44-63) The present invention relates to a method of preventing the accumulation of an electric charge by liquid hydrocarbons; to liquid hydrocarbons treated by this method, or more specifically to a method of preventing the accumulation of an electric charge by liquid hydrocarbons such as various kinds of petroleum fuel, dry-cleaning benzene, paint thinner, etc., by adding thereto some metallic salt of a non-alkaline metal selected from among amphoteric surface active agents having the following formulas:

RCONHOHzOHzN y CHzCOO X (I) %NOH RC HO NCH2 (CHR'CHR'A) H My OHzCOO x (11) (RNHCHR'CHzCOO) xM (III) OH (CHRCHRA) H R 1\'T (GHRCHRAMH My OHzCOO (IV) (where R denotes a hydrocarbon group with 8 to 22 carbon atoms; R is hydrogen or a lower alkyl group; A is oxygen or an imino group; M is a nonalkaline metal (i.e., a metal other than those in Group I of the long form of the periodic table of the elements); m, n are integers; and x, y are integers dependent on the valence of the nonalklaline mteal and such as to bring the bracketed group and the metal into stoichiometric proportion); and to liquid hydrocarbons to which some metallic salt of a nonalkaline metal selected from among the above-mentioned amphoteric surface active agents has been added.

The demand for petroleum and organic solvents has been on the increase in recent years. Meanwhile, a substantial part of the accidental fires and explosions thereof are presumably attributed to the discharge of static electricity. Petroleum and organic solvents accumulate an electric charge during transportation through a pipe-line, through agitation in tanks, or due to vibration while in transit in tank cars or the like. This is believed to result when the inner one of the double layers of electric charge formed near the vessel Wall moves relative to the other, and it is a well-known fact that the more violent the movement of the liquid, the greater the electric charge. Such accidents, therefore, may be prevented by eliminating such violent conditions as contribute to the accumulation of an electric charge, by avoiding the formation of an explosive gas mixture, or by assuring perfect grounding of the vessel. But petroleum fractions and some types of organic solvents have extremely low electric conductivity. For instance, gasoline and kerosene have a specific conductivity as low as 0.3 to 50 picomho/m. (10- /ohm- /m.); and the accumulated charge in such liquids may easily reach the critical limit at which it will discharge instead of leaking off. A most efiective way of facilitating leakage of the charge built up in such liquids is to increase their electric conductivity. For instance, A. Klinkenberg has reported that gasoline or kerosene, with its specific conductivity enhanced to 50-500 picomho/m., would be safe to a certain extent, and if the value were further raised to over 1,000 picomho/m., it would be safe enough under severe conditions (A. Klinkenberg and I. L. Van der Minne, Electrostatics in the Petroleum Industry).

The present inventors have discovered that if a metallic salt of a nonalkaline metal selected from among the amphoteric surface active agents with the above-mentioned general Formulas I to IV is added in the amount of 1 to 100 p.p.m. (from 1 to 100 kg. per 1000 m to such liquid hydrocarbons as various kinds of petroleum fuel, dry-cleaning benzene, paint thinner, etc., the electric conductivity of these liquids will be remarkably improved and the charge density of such liquids will be much lower than that of untreated liquids. The larger the proportion of added compounds to liquid hydrocarbons, the higher the electrical conductivity of these liquids will become. When, however, too much of said compounds is added, they will aflfect the dispersing agent in thepaint when said liquids are applied to paint, thereby causing sedimentation of the paint, and when applied to gasoline, will cause the deposit of solids on the cylinder. To prevent such troubles, the inventors have investigated the appropriate proportion of said compounds to liquid hydrocarbons and reached the conclusion that 1 to 100 p.p.m. will assure sufficient electric conductivity without adversely affecting the essential properties of said liquids. Particularly, when the addition exceeds 10 p.p.m., the electric conductivity will increase to over 1000 picomho/m., while less than 50 p.p.m. Will never afiect the essential properties of the liquids. Consequently, the optimum addition range is from 10 to 50 p.p.m. Unlike many other compounds in the prior art, when liquid hydrocarbons to which said compounds have been added are transported together with water in a pipeline, said compounds will not be extracted by the water, nor will they be emulsified and dispersed. Moreover, they contain very little sediment. For example, if gasoline to which said compounds have been added is employed, there will occur no resulting deposit on the cylinders and there will be no unfavorable effect on the essential properties of said gasoline. These are the advantages of the present invention.

In the metallic salt of a nonalkaline metal selected from among the above-mentioned amphoteric surface active agents with general Formulas I to IV, R is usually a hydrocarbon and is most easily synthesized with an excellent effect of electric charge prevention, when the number of carbon atoms ranges from 8 to 22; but even with the carbon atoms less than 8 or more than 22, a certain electric charge preventing effect is observable. R is hydrogen or a lower alkyl group, for example, a methyl group. A is oxygen or an imino group; and m, n are integers. Most desirably, m in the general Formulas I and II should be from 1 to 20, While the sum of m and n in IV should be 2 to 20. However, even at the value of over 20, the electric charge preventing effect exists. For instance, first ethylene oxide and then propylene oxide may be added to (CHRCHRA) M can be any nonalkaline metal, i.e. any metal not falling within group I in the long form of the periodic table of the elements; specifically, it can be magnesium, calcium, barium, lanthanum, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, gold, zinc, cadmium, mercury, aluminum, tin, lead or arsenic. Of these, the best are magnesium, calcium, barium, zinc, aluminum and lead, but others are also effective for preventing the accumulation of an electric charge. x, y are numbers dependent on the valence of the metal. Of course, the compound may be a mixture of two or more of the above-mentioned metallic salts. The compounds with the general Formulas I to IV can be synthesized as follows:

(l) The compounds with the general Formula I can be obtained by reacting polyamines such as ethylene diamine, diethylene triamine, or aminoethyl ethanolamine with a high molecular weight fatty or its esters or chlorides to produce amides, and reacting these amides as such or the reaction products of said amides and ethylene oxide, propylene oxide, or ethylene imine, with sodiummonochloride acetate to produce a soduim salt, and then effecting a double decomposition of the sodium salt with an inorganic salt of the nonalkaline metal. The following is an example of this process:

RCOOH NH2CH2CH2NHCH2CH2OH E RCONHCHzCHzNHCHzCHzOH NaOH RCONHCHzCHzNHCHzCHzOH ClCH2COON8 RCONHCHzCH2NCH2CH2OH NaCl H 0 ONE- 2RCONHCH2CH2NOH2CH2OH CaCl:

CHzCQ 0N2.

(RCONHCHzOHzNGHzCHzOHhCa QNaCl CHzCOO In the foregoing and in the ensuing formulae R represents a hydrocarbon group with 8 to 22 carbon atoms.

(2) The compounds having the general Formula II can be obtained by reacting polyamines like ethylene diamine, diethylene triamine or aminoethyl ethanolamine with a high molecular weight fatty acid or its esters or chlorides, to produce imidazol derivatives, and reacting said imidazol derivatives as they are (or the product obtained by reacting said imidazol derivatives with ethylene oxide, propylene oxide or ethyleneimine) with sodiummonochloride acetate to produce a sodium salt, and then effecting a double decomposition of said sodium salt with an inorganic salt of the nonalkaline metal.

The following is an example of this process:

N-CH, 2H2O RCOOH NHzCHzCHzNHCHrCHwH RC CHzCHzCH N-CHz CHZCHQOH CHnC OONa MgCh CHsOHaOH CHsCO ONa N-CH;

HO CHzCHaOH OHzCOO 2 RNHCH CH COOCH +NaOH+ RNHCH CH COONa+ CHgOH Mg ZNaCl (4) The compounds having the general Formula IV can be obtained by reacting a high class alkylamine with ethylene oxide, propylene oxide or ethyleneimine, and reacting the product of this reaction with sodiummonochloride acetate to produce a sodium salt and then effecting a double decomposition of said sodium salt with an inorganic salt of a nonalkaline metal. The following is an example of this process:

The liquid hydrocarbons, to which the proposed addition can be profitably made, have a boiling point in the range of about 30 to 300 C. and include gasoline, kerosene, light oil, benzene, toluene, xylene, chlorobenzene, nitrobenzene, bromobenzene, hexane, heptane, dimethylether, diethylether, dioxane, turpentine oil, carbon disulfide and similar substances; and even low boiling point liquefied gases such as liquefied propane and liquefied 'butane.

In the following, actual examples of executing the invented method are cited with the electric charge preventing efiect illustrated by the measurements of electric conductivity and charge density when inflammable liquids are treated with non-alkaline metal salts which are amphoteric surface active agents.

(1) The electrical conductivity was measured by means of an insulating oil testing electrode (TR-44 manufactured by Takeda Rikenkogyo K.K.); and the volume resistivity under a one minute application of v. was measured by means of a Vibrating Reed Electrometer (TR-84B manufactured by Takeda Rikenkogyo K.K.).

(2) The charge density was measured by a set-up consisting of a grounded stainless steel tank (1000 ml.), a stainless steel pipe (inner diameter 3 mm., length 50 cm.), a stopper, a Faraday cage and a Vibrating Reed Electrometer. First, 500 ml. of a sample liquid was poured into the tank, and after its flow rate had been adjusted by the stopper to 100 ml./min., was drained down the pipe to be received by the Faraday cage, where the magnitude of charge was measured.

Example 1 Metal salts of N-carboxymethyl-N-hydroxyethyl-N'- undecyloyl-ethylenediamine having thet following structural formula falling within the scope of general Formula I:

[011E230ONHCHQCH2NCH2CH2OH1M CHzCOO x were added respectively to gasoline, jet fuel, kerosene, light oil, benzol, toluol, and xylol (all produced by Mitsubishi Petroleum). The measured values of electric conductivity and charge density are cited below.

4.0501608058250750526 EAmZO OMZZomQ- QLZEZKwQQWOm- 1 1 1 1 (VII) L7 3 &7 ta5 0 1 7 aL ity and a lower 2NH21M Addition (kg/1,000 111.

&Ldd2 omLzdd 3 0 i7 5 245 7 e7 3 5 5 d2 L dL7 5 N carboXymethyl-N- ine having the following structhin the scope of general Hiooo Addition (kg/1,000 111.)

Charge density (mierocoulomb/mfi) None Example 3 Charge density (microcoulomb/mfi) None [017E350 ONHCHzCHzNCH CH QUIDS TO WHICH COMPOUNDS HAVING THE Electric conductivity (picomho/m.)

Addition (kg/1,000 m!) None TURAL FORMULA V HAVE BEEN ADDED X (VI) no 45 were added respectively to gasoline, et fuel, kerosene,

FORMULA VI HAVE BEEN ADDED.

Electric conductivity (picomho/m.)

Addition (kg/1,000 111.

None

Inflammable organic liquid Gaso1ine having the following struc- (IIHZCOQ Example 2 inc Inflammable organic liquid TABLE 1.ELECTRIC CONDUCTIVITY AND CHARGE DENSITY OF LIQUIDS TO WHICH COMPOUNDS WITH THE STRUC- Mg x=2 Cax 2.

Ba x=2 Zn x=2 Pb x=2 Gasoline.

As seen from Table 1, the inflammable organic liquids 30 treated with compounds having the Formula V have a considerably higher electric conductivity and a lower charge density than untreated ones.

Metal salts of N-aminoethyl-N-carb0Xymethyl-N'- heptadecyloyl-ethylenediam (QUEBECONHCH2CH2NCH2CH2OH ght oil, benzol, toluol and xylol (all produced b TABLE 2.ELECTRIC GONDUGTIVITY AND CHARGE DENSITY 0F LI tural formula falling within the scope of general Formula I:

were added respectively to gasoline, jet fuel, kerosene, 11'

Mitsubishi Petroleum). The measured values of elect conductivity and charge density are cited below.

Mg x=2 Oax=2 Ba x=2 Zn x=2 Al x=2 Addition (kg./l,000 111.

, kerosene,

he scope of general Formula Addition (kg/1,000 in!) Charge density (microcoulomb/mfi) None adlaoaaa 5 5 3 a5 7 Example 5 l-imidazoline having the following struc- N-CH:

/N CH2 HO l CHaCHzOH CHICOO toluol and xylol (all produced by Mit- Charge density (microcoulomblm!) None As seen from Table 4, the inflammable organic liquids treated with compounds with the Formula VIII have a Electric conductivity (plcomho/m.)

Addition (kg/1,000 mfi) 'benzol considerably higher electric conductivity and a lower charge density than untreated ones.

Metal salts of N-carboXymethyl-N-hydroxyl-N-hydroxyethyl-Z-heptadecy tural formula falling within t were added respectively to gasoline, jet fuel light oil,

BEEN ADDED VII have a d a lower follow- (VIII) FORMULA VIII HAVE Electric conductivity (picomhc/m.)

Addition (kg.l1,000 m!) None N hydroxyl-N- TABLE 3ELECTRIC CONDUCTIVI'IY AND CHARGE DENSITY 0F LIQUIDS TO WHICH COMPOUNDS HAVING THE FORMULA VII HAVE BEEN ADDED Inflammabie organic liquid Gasoline.-

the inflammable organic liquids Example 4 N-CH1 N-(LHa Ho c11,cHioH CH2COO toluol and Xylol (all produced -by The measured values of electric Mitsubishi Petroleum). The measured values of electric conductivity and charge density are cited below.

As seen from Table 3, treated with compounds with the Formula Metal salts of N carboxymethyl hydroxyethyl-Z-undecyl imidazoline having the TABLE 4.ELECTRIC CONDUC'IIVITY AND CHARGE DENSITY OF LIQUIDS TO WHICH COMPOUNDS HAVING THE considerably higher electric conductivity an charge density than untreated ones.

ing structural formula falling within the scope of general Formula II:

were added respectively to gasoline, jet fuel, kerosene, light oil, benzol,

Mitsubishi Petroleum).

conductivity and charge density are cited below.

a I m I q I h C n u m I I m m I I .III II I m I I I I I I III a IIIIIIT I I I mmnrmmrnnm 5 0m I.m1 1 I SOOISOO S I S llOOl u muf h f h u m mammn emtm wtn wnmmfl i .1 I GKBTGKBTMKLXRKLXGBTX I I I I I I I I I I 2 2 I2 2 II II II n I H X x X x a a n b M C B Z P Addition (kg./1,000 111.

Addition (kg/1,000 111.)

Charge density (microcoulomb/mfi) None Charge density (microcoulomb/mfl) None y and charge density are cited below.

light oil, benzol, toluol and xylol (all produced by Mitsubishi Petroleum). The measured values of electric con- 154891 052 29154 n807479746m -w877858 LLZLLLLLLLLLLLLLLLII ND CHARGE DENSITY OF LIQUIDS TO WHICH Addition (kg./l,000 111.

FORMULA X HAVE BEEN ADDED Addition (kg/1,000 111.

Electric conductivity (picomho/m.)

None

5.0505048500450045004 i mflld lomaaw wlafimizamailam 11 1 1 1 Electric conductivity (picomho/m.)

COMPOUNDS HAVING THE FORMULA IX HAVE BEEN ADDED Inflammable organic liquid Kerosene.--"

TABLE 5.ELECTRIC CONDUCTIVITY A subishi Petroleum). The measured values of electric conductivity and movable charge voltage are cited below.

As seen from Table 5, the inflammable organic liquids ductivit treated with compounds with the Formula IX have a TABLE 6.ELECTRIO CONDUOTIVITY AND CHARGE DENSITY OF LIQUIDS TO WHICH COMPOUNDS HAVING THE ganic liquids y and a lower Example 7 Metal salts of dodecylam-ino propionic acid having the iollowin falling Within the scope As seen from Table 6, the inflammable or treated with compounds having the Formula X have a considerably higer electric conductivit charge density than untreated ones.

g structural formula of general formula HI: 7O

(C H NHCH CH COO) M were added respectively to gasoline, jet fuel, kerosene,

Example 6 Metal salts of N-carboxymethyl-N-hydroxyl-N-fi-hydroxyethoxyethyl-Z-heptadecyl-imidazoline having the fol- 5 lowing structural formula falling within the scope of general Formula III CHzOHzO GHzCHiOH OHzO O O N-CH, Cl7

N-CH: 1

were added respectively to gasoline; jet fuel, kerosene, ll ht oil, benzol, toluol and xylol (all produced by Mitconsiderably higher electric conductivity and a lower charge density than untreated ones.

(XIII) 084 00203502420808015 65 7 47rm5 4 5 6 6 5 &&&3 &nw9 7 Addition (kg/1,000 m!) Addition (kg/1,000 m!) Charge density (microcoulomb/m') None Example 9 (IE (CHzCHzQ)mH N\ l (CHzC H2O) nH CHzC O 0 Charge density (microcoulomb/mfi) None la falling within the scope of general Formula As seen from Table 8, the inflammable organic liquids treated with compounds with the Formula XII have a considerably higher electric conductivity and a lower charge density than untreated ones.

Metal salts of bis (polyoxyethylene)-dodecyl-carboxytural formu IV:

FORMULA XI Electric conductivity (picomho/rn.)

Addition (kg/1,000 m!) N one iquids o methyl-ammonium hydroxyde having the following strucductivity FORMULA XII HAVE BEEN ADDED Electric conductivity (plcornho/m.)

Addition (kg/1,000 m3) None Inflammable organic liquid g the Formula XI have ric conductivity and a lower Example 8 duced by Mitsubishi Inflammabie organic liquid TABLE 7.ELECTRIC CONDUCTIVITY AND CHARGE DENSITY OF LIQUIDS ADDED WITH COMPOUNDS WITH THE subishi Petroleum) the measured values of electric conductivity and charge density are cited below.

n F F x F a b 1 M o m P A Gasoline Kerosene As seen from Table 7, the inflammable organic 1 treated with compounds havin a considerably higher elect charge density than untreated ones.

Metal salts of octadecylamino propionic acid having the following structural formula falling within the scope of general formula III (C H NHCH CH C0O) M toluol and xylol (all pro The measured values of electric con and charge density are cited below.

TABLE 8.-ELECTBIC CONDUCTIVITY AND CHARGE DENSITY OF LIQUIDS TO WHICH COMPOUNDS HAVING THE were added respectively to gasoline, kerosene, light oil, 45 benzol, Petroleum) Xylol.-

- 13 14 were added respectively to gasoline, kerosene, light oil, As seen from Table 10, the inflammable organic liquids benzol, and toluol (all produced by Mitsubishi Petrowhich have been treated with compounds with the For leum). The measured values of electric conductivity and mula XIV have a considerably higher electric conductivity charge density are cited below. and a lower charge density than untreated ones.

TABLE 9.ELECTRIC CONDUCTIVITY AND CHARGE DENSITY OF LIQUIDS TO WHICH OOMPO UNDS HAVING THE V FQRMULA XIII HAVE BEEN ADDED Electric conductivity (picomho/m.) Charge density (microcoulomb/md) M Infiammable organic liquid Addition (kg./1,000 111. Addition (kg./1,000 mfi) None 1 10 100 None 1 10 100 Mg x=2 Gasoline 3. 5 570 1, 700 3, 820 43.0 31. 4 17. 5 9. Kerosene" 15. 0 520 1, 810 3, 400 48. 29. 8 16. 1 8. 5 Benzol. 2.0 640 1, 860 4,050 62. 5 30.0 14. 8 5. 2 Toluol 3. 4 550 1, 800 3, 670 48. 8 27. 5 12. 9 7. 0 Ca x=2 Gasoline 3. 5 620 1, 410 2, 950 43.0 20. 8 13. 5 2. 8 Kerosene 15. 0 660 1, 550 3, 270 48. 5 26. 2 16. 9 6. 5 2. 0 580 1, 470 3, 310 62. 5 25. 9 11. 6 7. 2 3. 4 700 1, 860 3, 540 48. 8 22. 3 13. 7 7. 2 3. 5 260 1, 050 2, 920 43. 0 21. 6 10. 9 8. 8 15. 0 350 1, 120 2, 600 48. 5 24. 5 14. 6 2. 6 10. 5 500 1, 300 2, 840 52. 5 25. 2 11. 5 3. 6 2. 0 470 1, 190 3, 050 62. 5 25. 8 12. 1 3. 0 3. 5 420 1, 740 2, 500 43. 0 30. 3 18. 1 2. 5 15. 0 550 1, 420 2, 610 48. 5 28. 1 17. 0 7. 0 10. 5 390 1, 500 2, 900 52. 5 26. 0- 18. 9 4. 2 2. 0 690 1, 640 2, 840 62. 5 27. 6 14. 1 6. 1

As seen from Table 9, the inflammable organic liquids Example 11 which have been treated with compounds having the Formula XIII have a considerably higher electric con- Me alsalts of his (polyoxyethylene)-octadecyl-carboxyductivity and a lower charge density than untreated ones. methyl-ammonium hydroxide having the following struc- Example 10 tural formula within the scope of general Formula IV:

Compounds having the following structural formula falling within the scope of general Formula IV:

OH Z z M OH (CH2GH:O)mH CHHMIlI/ CH1BH37N (OH OH O) H (CHZCHzOhH 0132000 2 n x (XV) H2000 x (XIV) 4) were added respectively to gasoline, kerosene, benzol and toluol (all produced by Mitsubishi Petroleum). The meas- I ured values of electric conductivity and charge density were added respectively to gasoline, et fuel, kerosene, are given below. light oil, benzol, toluol, and xylol (all produced by Mitsu- .E TRIO ONDUDTIVITY AND CHARGE DENSITY OF LIQUIDS TO WHICH COMPOUNDS HAVING THE TABLE 10 LEG C FORMULA XIVHAVE BEEN ADDED Electric conductivity (picomho/m.) Charge density (microcoulomb/mfi) M Infiammable or anic li uid g q Addition (kg/1,000 mfi) Addition (kg/1,000 m!) None 1 10 I None 1. 10 100 3. 5 460 2, 600 3, 750 43. 0 28. 5 10. 2 6. 5 Mg x 2 15. 0 500 2, a, 540 48. 5 20.0 12. 5 4. 7 2. 0 470 2, 230 3, 200 62. 5 32. 1 11. 6 5. 0 3. 4 610 2, 540 3, 360 48. 8 30. 7 12. 7 5.0 Ca x=2 3. 5 720 2,000 3,120 43.0 18.5 11.0 8. 2 15.0 690 1, 940 3,060 48. 5 20. 9 12. 1 5. 2 2. 0 770 2, 100 3, 100 62. 5 26. 2 l0. 8 7. 0 3. 4 730 2, 100 3, 370 48.8 21. 0 l3. 5 8. 2 Zn x=2 3. 5 910 1, 800 2, 950 43.0 26. 4 17. 0 11.2 15.0 790 1, 920 2, 910 48.5 27. 5 18.0 7. 5 2. 0 820 1, 800 2, 860 62. 5 25. 0 15. 6 9. 1 3. 4 850 2, 000 2, 850 48.8 20.6 12. 9 8.0 Pb x=2 3. 5 750 1,590 2, 600 43.0 27.0 18. 4 12.0 15.0 700 1, 710 2, 740 48.5 22. s 16. s 6.9 2. 0 680 1, 750 2, 900 62. 5 23. 8 l2. 3 7. 5 3. 4 760 l, 640 2, 850 48.8 20.4 11. 8 8. 4

Addition (kg/1,000 II perties comprising an in bon and effective antistatic Charge density (microcoulomb/mfl) None Formula XVI have a considerably higher electric conductivity and a lower charge density than untreated ones.

What is claimed is: 1. An inflammable organic liquid hydrocar position having antistatic pro mable organic liquid hydrocar amounts of at least one metallic salt of a nonalkaline metal which is an amphoteric surface active agent with respect to said liquid and is selected from the group consting of:

FORMULA XV HAVE BEEN ADDED Electric conductivity (picomho/m.)

Addition (kg/1,000 mfi) None below.

pounds with the electric conducd ones.

the following 35 Si The measured values of electric con- Infiammable organic liquid Kerosene" Toluol.

Kerosene...

the inflammable organic liq- Example 12 bishi Petroleum). ductivity and charge density are given TABLE 11.ELECTRIC CONDUGTIVITY AND CHARGE DENSITY 0F LIQUIDS TO WHICH COMPOUNDS HAVING THE As seen from Table 11, uids which have been treated with com Metal salts of bis (polyoxypropylene)-octadecyl-carammonium hydroxide having Formula XV have a considerably higher tivity and a lower charge density than untreate boxymethyl- [RCONHCHaCHaN 0 5 4 A m w F X l a r e n e 0: m M x 1i a a a W a W O a n n n n e fl w h n H t w n C n H m t .1 0 s m w u rllli. m I O f 1 2 3 M m an a nm 0 (III 5311.. IIIIMIMIIUBMH Addition (kg/1,000 mfi) below.

FORMULA XVI HAVE BEEN ADDED Electric conductivity (picomholm.)

None

toluol and xylol (all produced by Mitsuhe measured volumes of electric con- 50 Inflammable organic liquid Xylol.

were added respectively to gasoline, jet fuel, kerosene,

light oil, benzol,

bishi Petroleum). T

ductivity and charge density are given TABLE 12.ELECTRIC CONDUCTIVITY AND CHARGE DENSITY or LIQUIDS TO WHICH COMPOUNDS HAVING THE As seen from Table 12, the inflammable organic liquids where R is a hydrocarbon group with 8 to 20 carbon ds having the 75 atoms; R is selected from the group consisting of hydrowhich have been treated with compoun 1 7 gen and a lower alkyl; A is selected from the group consisting of oxygen and an imino; M is a nonalkaline metal; m and n are integers; and x and y are integers dependent on the valence of the nonalkaline metal which bring the bracketed group and the metal into stoichiometric proportion.

2. The composition of claim 1 wherein the amount of said amphoteric surface active agent present in said composition is from 1 to 100 p.p.m.

3. The inflammable organic liquid hydrocarbon composition of claim 1 comprising from 10 to 50 p.p.m. of said metallic salt of a nonalkaline metal.

4. The inflammable organic liquid hydrocarbon composition of claim 1 in which at least one of said metallic salts of a nonalkaline metal has the formula (CHR CHR A)mH] [RCONHCHzCHzN M CHzGOO where R is a hydrocarbon with 8 to 22 carbon atoms; R is selected from the group consisting of hydrogen and a lower alkyl; A is selected from the group consisting of oxygen and an imino group; M is a nonalkaline metal; In is an integer; and x, y are integers dependent on the valence of the nonalkaline metal.

6. The inflammable organic liquid hydrocarbon composition of claim 1 in which at least one of said metallic salts of a nonalkaline metal has the formula OH CHR'CHRA) H I J RN CHR'CHR'A) H CHzCOO x where R is a hydrocarbon with 8 to 22 carbon atoms; R is selected from the group consisting of hydrogen and a lower alkyl; A is selected from the group consisting of oxygen and an imino group; M in a nonalkaline metal; m, n are integers; and x, y are integers dependent on the valence of the nonalkaline metal.

References Cited UNITED STATES PATENTS 2,790,779 4/ 1957 Spivack et a1. 3,116,125 12/1963 Bartlett et a1.

FOREIGN PATENTS 921,032 3/ 1963 Great Britain.

DANIEL E. WYMAN, Primary Examiner.

W. H. CANNON, Assistant Examiner. 

1. AN INFLAMMABLE ORGANIC LIQUID HYDROCARBON COMPOSITION HAVING ANTISTATIC PROPERTIES COMPRISING AN INFLAMMABLE ORGANIC LIQUID HYDROCARBON AND EFFECTIVE ANTISATIC AMOUNTS OF AT LEAST ONE METALLIC SALT OF A NONALKALINE METAL WHICH IS AN AMPHOTERIC SURFACE ACTIVE AGENT WITH RESPECT TO SAID LIQUID AND IS SELECTED FROM THE GROUP CONSISTING OF: 